Thermosettable resin compositions

ABSTRACT

A novel polyfunctional maleimide-based thermosettable resin composition comprising: (a) at least one polyfunctional maleimide compound selected from the group consisting of bismaleimide and polymaleimide, and (b) at least one ether derivative of an alkenylphenol.

This application is a division, of application Ser. No. 07/086,137,filed 8/17/87 now U.S. Pat. No. 4,962,16.

FIELD OF THE INVENTION

This invention concerns novel polyfunctional maleimide-basedthermosettable resin compositions having improved processing capability.This invention further concerns prepregs and composite materialsmanufactured from such resin compositions.

BACKGROUND OF THE INVENTION

Polyfunctional maleimide-based thermosettable resins, such asbismaleimide-based or polymaleimide-based resins, are known to haveexcellent heat resistance properties and thus are particularly suitedfor use in applications such as the manufacture of impregnating resinsfor use in high temperature resistant advanced fiber reinforcedcomposite have played a significant role in the manufacture of primary,secondary and empennage structures for the aerospace industry inaddition to applications in the automobile and electronics industry. Theuse of such resins, however, has been limited due to processingdifficulties, since most commercially available bismaleimides andpolymaleimides are high melting solids.

It is, therefore, an object of this invention to provide a novelimproved polyfunctional maleimide-based thermosettable resin compositionhaving improved processing characteristics. It is a further object ofthis invention to provide prepregs and composite materials manufacturedfrom such resin compositions.

SUMMARY OF THE INVENTION

It has now been found that polyfunctional maleimide-based thermosettableresin compositions having improved processing capability can be providedby a composition comprising: (a) at least one polyfunctional maleimidecompound selected from the group consisting of bismaleimide andpolymaleimide, and (b) at least one ether derivative of analkenylphenol.

This invention is further illustrated by the following detaileddescription.

DETAILED DESCRIPTION OF THE INVENTION

In accordance with the invention, a thermosettable resin composition isprovided comprising: (a) at least one polyfunctional maleimide compoundselected from the group consisting of (i) bismaleimide and (ii)polymaleimide, having the respective general formulas: ##STR1## where Ais a divalent organic radical of at least two carbon atoms, and R₁ -R₁₀are the same or different hydrogen atoms, halogen atoms, cyano groups,straight-chain or branched, saturated or unsaturated alkyl radicalshaving from 1 to 6 carbon atoms, phenyl radicals, or substituted phenylradicals having one or more substituents selected from straight-chain orbranched, substituted or unsubstituted alkyl radicals, halogen atoms,cyano groups, and where n is a positive integer; and, (b) at least oneether derivative of alkenylphenol having the general formula: ##STR2##wherein X is

    --CH═CH--R, or

    --CH.sub.2 --CH═CH--R; and

wherein Y is ##STR3## where R is defined as R₁ -R₁₀ in formulas (i) and(ii) above, and where R' is either a divalent organic radical of atleast two carbon atoms selected from aliphatic, alicyclic, aromatic orheterocyclic radicals or a divalent organic radical of the generalformula: ##STR4## and where R is defined as R₁ -R₁₀ in formulas (i) and(ii) above, and where n is a positive integer; and where the oxygen atomthat connects Y and the aromatic ring can also be replaced by a sulfuratom.

Any polyfunctional maleimide compound known in the prior art may besuitable for this invention including, for example, commerciallyavailable bismaleimide resins from Technochemie, Ciba-Geigy andMitsubishi such as bismaleimides of methylene dianiline, diamino benzeneand diamino toluene. Further, polyfunctional maleimide compounds such asdisclosed in U.S. Pat. Nos. 4,463,147; 4,389,516; 4,298,720; 4,179,551;4,100,140; and 4,035,345, of which are expressly incorporated herein,are suitable for use in this invention.

Specific examples of such polyfunctional maleimide compounds suitablefor use in this invention include:

N,N'-4,4'-diphenylmethane-bis-maleimide,

N,N'-ethylene-bis-maleimide,

N,N'-ethylene-bis(2-methylmaleimide),

N,N'-trimethylene-bis-maleimide,

N,N'-tetramethylene-bis-maleimide,

N,N'-hexamethylene-bis-maleimide,

N,N'-1,4,-cyclohexylene-bis-maleimide,

N,N'-meta-phenylene-bis-maleimide,

N,N'-para-phenylene-bis-maleimide,

N,N'-2,4-toluene-bis-maleimide,

N,N'-2,6-toluene-bis-maleimide,

N,N'-4,4'-diphenylmethane-bis-maleimide,

N,N'-4,4'-3,3'-dichloro-diphenylmethane-bis-maleimide,

N,N'-4,4'-diphenyl-ether-bis-maleimide,

N,N'-4,4'-diphenylsuphone-bis-maleimide,

N,N'-4,4'-dicyclohexylmethane-bis-maleimide,

N,N'-α,α'-4,4'-dimethylenecyclohexane-bis-maleimide,

N,N'-meta-xylene-bis-maleimide,

N,N'-para-xylene-bis-maleimide,

N,N'-4,4'-diphenyl-cyclohexane-bis-maleimide,

N,N'-meta-phenylene-bis-tetrahydrophthalimide,

N,N'-4,4'-diphenylmethane-bis-citraconimide,

N,N'-4,4'-2,2-diphenylpropane-bis-maleimide,

N,N'-4,4-1,1-diphenyl-propane-bis-maleimide,

N,N'-4,4'-triphenylmethane-bis-maleimide,

N,N'-α,α'-1,3-dipropylene-5,5-dimethyl-hydantoin-bis-maleimide,

N,N'-4,4'-(1,1,1-triphenyl ethane)-bis-maleimide,

N,N'-3,5-triazole-1,2,4-bis-maleimide,

N,N'-4,4'-diphenyl-methane-bis-itaconimide,

N,N'-para-phenylene-bis-itaconimide,

N,N'-4,4'-diphenylmethane-bis-dimethyl-maleimide,

N,N'-4,4'-2,2-diphenylpropane-bis-dimethylmaleimide,

N,N'-hexamethylene-bis-dimethyl-maleimide,

N,N'-4,4'-(diphenyl ether)-bis-dimethyl-maleimide,

N,N'-4,4'-diphenylsulphone-bis-dimethylmaleimide,

N,N'-(oxydi-para-phenylene)-bis-maleimide,

N,N'-(oxydi-para-phenylene)-bis-(2-methyl-maleimide),

N,N'-(methylenedi-para-phenylene)bis-maleimide,

N,N'-(methylenedi-para-phenylene)bis-(2-methylmaleimide),

N,N'-(methylenedi-para-phenylene)bis(2-phenylmaleimide),

N,N'-(sulfonyldi-para-phenylene)bis-maleimide,

N,N'-(thiodi-para-phenylene)bis-maleimide,

N,N'-(dithiodi-para-phenylene)bis-maleimide,

N,N'-(sulfonyldi-meta-phenylene)bis-maleimide,

N,N'-(ortho, para-isopropylidenediphenylene)bis-maleimide,

N,N'-(isopropylidenedi-para-phenylene)bis-maleimide,

N,N'-(ortho,para-cyclohexylidenediphenylene)bis-maleimide,

N,N'-(cyclohexylidendi-para-phenylene)bis-maleimide,

N,N'-(ethylenedi-para-phenylene)bis-maleimide,

N,N'-(4,4"-para-triphenylene)bis-maleimide,

N,N'-(para-phenylenedioxydi-para-phenylene)bis-maleimide,

N,N'-(methylenedi-para-phenylene)bis-(2,3,-dichloromaleimide),

and N,N'-(oxydi-para-phenylene)bis(2-chloromaleimide).

The thermosettable resin compositions of this invention, of course, cancomprise more than one type of polyfunctional maleimide compound as setforth above, and may comprise a mixture of several such compounds.

It is preferable, however, to useN,N'-4,4'-diphenylmethane-bis-maleimide in this invention.

Specific examples of ether derivatives of alkenylphenols for use in thisinvention include:

1,4-bis-eugenoxybutane,

1,3-bis-eugenoxypropane,

1,3-bis-isoeugenoxypropane,

α,α'-bis(ortho-propenylphenoxy)-para-xylene,

1,3-bis-(isoeugenoxy)-2-hydroxy-propane,

1,3-bis-(ortho-propenylphenoxy)propane,

α,α'-bis-(2-propenylphenoxy)-meta-xylene,

α,α'-bis-eugenoxy-para-xylene,

1,5,-bis-eugenoxypentane,

1,6-bis-eugenoxyhexane,

α,α'-bis-isoeugenoxy-para-xylene,

α,α'-bis-eugenoxy-meta-xylene,

α,α'-bis-(ortho-propenylphenoxy)-meta-xylene,

bis-(ortho-propenylphenoxy)-meta-xylene, and,

para-bis(ortho-propenylphenoxy)-meta-xylene.

The aforementioned ether derivatives of alkenylphenol can be preparedfrom nucleophilic substitution of eugenol, isoeugenol, allylphenol orpropenylphenol in the presence of an alkali metal hydroxide and suitablesolvents at temperatures ranging from about ambient to about 150° C. toform the alkenyl ethers therefrom via condensation (elimination of thealkali metal and ether formation).

The following examples more fully illustrate the preparation of suchether derivatives of alkenylphenol as set forth above. They are notintended, however, to limit the present invention in any way thereto.

EXAMPLE I

1,4-bis-eugenoxybutane is prepared according to the following procedure.

100.5 grams (0.61 moles) of eugenol and 1 liter of isopropyl alcohol(IPA) are added to a flask equipped with a mechanical stirrer, anitrogen inlet and a bubbler. After sparging with nitrogen for 15minutes, an aqueous potassium hydroxide solution of 7.93millieqivalents/gram (76.5 grams, 0.61 moles) is added to the contentsof the flask. The mixture is stirred for 15 minutes, then 60.6 grams of1,4-dibromobutane (0.28 moles) and 4 milliliters of tricaprylyl methylammonium chloride is added thereto. The resulting mixture is thenstirred at 45° C. for 16 hours, during which time a precipitate forms.Filtration thereof followed by subsequent aqueous washing fields 89grams of a white powder (83% yield) of melting point 101°-102° C.

EXAMPLE II

1,3-bis-eugenoxypropane is prepared in a procedure similar to Example I,except that 98.5 grams (0.60 mole) of eugenol is employed along with60.6 grams (0.30 mole) of 1,3-dibromopropane to yield 80 grams (72%yield) of a crystalline material having a melting point of 79°-80° C.

EXAMPLE III

1,3-bis-isoeugenoxypropane is prepared in a procedure similar to ExampleI, except that 100 grams (0.61 mole) of isoeugenol is employed alongwith 65.5 grams (0.30 mole) of 1,3-dibromopropane to yield 72 grams (72%yield) of a crystalline material with melting point 103°-106° C.

EXAMPLE IV

α,α'-bis-(ortho-propenylphenoxy)-para-xylene is prepared in a proceduresimilar to Example I, except that 459.3 grams (3.4 moles) of2-allylphenol is employed along with 300 grams (1.7 mole) ofdichloro-para-xylene to yield 597 grams (95% yield) of a whitecrystalline solid having a melting point of 50°-53° C.

EXAMPLE V

1,3-bis-(isoeugenoxy)-2-hydroxy-propane is prepared in a proceduresimilar to Example I, except that 300 grams (1.83 moles) of isoeugenolis employed along with 199 grams (0.91 mole) of 1,3-dibromo-2-propanolto give a product that is precipitated in hexane. 262 grams of anoff-white powder is recovered having a melting point of 79°-82° C.

EXAMPLE VI

1,3-bis(ortho-propenylphenoxy)propane is prepared in a procedure similarto Example I, except that 537 grams (4.0 moles) of prophenyl phenol isemployed along with 403 grams (1.98 moles) of 1,3-dibromo-propane toproduct a reaction mixture extracted with methylene chloride and driedover magnesium sulfate, then vacuum distilled to give 311 grams (50%yield) of a solid with melting point 45°-48° C.

EXAMPLE VII

α,α'-bis-(2-propenylphenoxy)-meta-xylene is prepared in a processsimilar to Example I, except that 383 grams (2.86 mole) ofpropenylphenol is employed along with 250 grams (1.43 moles) ofα,α'-dichloro-meta-xylene to give a reaction product extracted withmethylene chloride, washed with potassium hydroxide and dried overmagnesium sulfate, then vacuum distilled at 80° C. to yield 407 grams ofa viscous liquid (80% yield).

EXAMPLE VIII

α,α'bis-eugenoxy-para-xylene is prepared in a procedure similar toExample I, except that 62.2 grams (0.38 moles) of eugenol is employedalong with 50 grams (0.19 mole) of α,α'-dibromo-para-xylene to produce80.3 grams of a solid (98% yield) having a melting point of 106°-107° C.

EXAMPLE IX

1,5-bis-eugenoxypentane is prepared in a procedure similar to Example I,except that 100 grams (0.61 mole) of eugenol is employed along with 70grams (0.30 mole) of 1,5-dibromopentane to produce 98.4 grams (83%yield) of a solid having melting point 68°-69° C.

EXAMPLE X

1,6-bis-eugenoxyhexane is prepared in a procedure similar to Example I,except that 100 grams (0.61 mole) of eugenol is employed along with 74.3grams (0.30 mole) 1,6-dibromohexane to give 101 grams (82% yield) of asolid with melting point 72°-73° C.

EXAMPLE XI

α,α'-bis-isoeugenoxy-para-xylene is prepared in a procedure similar toExample I, except that 68.8 grams (0.42 mole) of isoeugenol is employedwith 55.3 grams (0.21 mole) of α,α'-dibromo-para-xylene to give 80 grams(89% yield) of a solid with melting point of 136°-140° C.

EXAMPLE XII

α,α'-bis-eugenoxy-meta-xylene is prepared in a procedure similar toExample I, except that 1.76 grams (1.07 mole) of eugenol is employedalong with 94 grams (0.54 mole) of α,α'-dichloro-meta-xylene to give 208grams (90% yield) of a solid with melting point 49°-50° C.

EXAMPLE XIII

α,α'-bis(ortho-propenylphenoxy)-para-xylene is prepared according to thefollowing procedure.

A mixture of 200 grams (0.76 mole) of α,α'-dibromo-para-xylene, 240grams (1.8 mole) of ortho-propenylphenol, 300 grams (2.2 moles) ofpotassium carbonate, 10 milliliters of tricaprylyl methyl ammoniumchloride, and 3 liters of acetone is heated to boiling for 24 hours. Theinorganic salt is filtered and washed 200 milliliters of acetone, thenthe organic portion is extracted with a 1M sodium hydroxide solution toremove excess phenol, followed by aqueous washing. The organic layer isthen dried over sodium sulfate and the solvent removed under vacuum togive 250 grams (80% yield) of a liquid.

Additionally, the thermosettable resin compositions of this inventionmay contain more than one type of alkenylphenol ether derivatives as setout above, and may comprise several such compounds.

Of the aforementioned alkenylphenol ether derivatives,α,α'-bis-(ortho-propenylphenoxy)-para-xylene andα,α'-bis-(2-propenylphenoxy)-meta-xylene are preferred.

In accordance with this invention, the alkenylphenol ether derivativescan be reacted with the various polyfunctional maleimide compoundsheretofore mentioned to produce a readily processable resin matrixhaving high heat resistance.

Broadly speaking, it is believed that the reaction mechanism of thepolyfunctional maleimide compounds and the ether derivatives ofalkenylphenol can proceed through a (1) free radical type reaction or a(2) ene type reaction or a (3) diels-alder type reaction of the twocompounds, depending on the position of unsaturation on thealkenylphenol ether derivative. A subsequent diels-adler type reactionmay follow depending upon reaction conditions. It is to be understood,however, that this invention is not intended to be limited in any way tosuch reactions. The above-mentioned reactions, which of course, are wellknown in the prior art can be represented as follows: ##STR5##

In preparing cured resin matrixes from reaction mixtures ofpolyfunctional maleimides and alkenylphenol ether derivatives, suchmixture compositions are subject to wide variation depending upon, forexample, the particular polyfunctional maleimides and alkenylphenolether derivatives employed therein, and the specific resin end usescontemplated. Accordingly, weight percent ratios of polyfunctionalmaleimide to alkenylphenol ether derivatives will range generally fromabout 0.5:1 to about 10:1, and preferably from about 1.3:1 to about2.0:1.

Cure temperatures can range from about ambient to about 270° C. over atime span from about 2 hours to in excess of 24 hours. A preferredcuring schedule is as follows: 3 hours at 130° C., 2 hours at 150° C.and 5 hours at 250° C. A more preferable curing schedule is 2 hours at180° C. and 5 hours at 250° C. Optionally, curing may be accomplished inan autoclave under pressure, followed by a post cure according toschedules as set forth above. Of course, other curing schedules may beemployed, again, depending upon the particular polyfunctionalmaleimide-alkenylphenol ether derivative mixture employed and specificresin end uses contemplated.

The curable polyfunctional maleimide components of this invention arenormally provided to the uncured reaction mixture in a solvent freestate, e.g., a solid form total maleimide resin. However, non-reactivesolvents may be employed wherein the maleimide component can be used inthe form of a solution. Examples of suitable solvents includeN-methyl-2-pyrrolidone, dimethylformamide, dimethylacetamide,dimethylsulfoxide, dioxane, acetone, methyl ethyl ketone,tetrahydrofuran, cellosolve, methyl acetate, ethyl acetate, chloroform,benzene, toluene, xylene, chlorobenzene, and tetramethyl urea.

Accordingly, the total uncured thermosettable resin composition mixtureof this invention comprising the polyfunctional maleimide andalkenylphenol ether derivative compounds can be used in the form of asolution by dissolving the mixture in a solvent such as mentioned above.

Depending upon a particular application, any of the thermosettable resincompositions of this invention can be admixed with one or moreadditional components to modify the properties of the cured resin matrixend product, provided that such additives do not adversely affect cure.Examples of such components include inorganic fillers such as silica,silica glass, clay, aluminum hydroxide, asbestos, mica, gypsum, kaolin,cement, talc, calcium carbonate and the like. In similar fashion,catalysts, stabilizers, free radical initiators, tackifiers,antioxidants, plasticizers, pigments, dyestuffs, mold release agents andflame retardant compounds, may be added to the thermosettable resincompositions of this invention. Still further, other components whichcan be added to the resin compositions of this invention to optimizesaid resins for various end uses include reactive rubbers andthermoplastics.

Thermosettable resin compositions of this invention can be used as animpregnating resin varnish to coat continuous (filimentary) fibers suchas carbon (graphite), for example, high-performance polyacrylonitrile(pan)-based carbon fibers and pitch-based carbon fibers, or, glass,boron, silica, ceramic, silicon carbide, aluminum oxide and other metaloxide fibers, polybenzimidazole, polyethylene, bicomponent polyethyleneand polypropylene fibers, polyimide, or mixtures thereof to manufactureprepregs. In addition, fibers such as alumina-boria-silica, producedfrom a combination of the oxides of aluminum, boron and silicon andavailable from the Minnesota Mining and Manufacturing Company, PBZ afamily of heterocyclic, rigid rod and chain extended polymers availablefrom the Dow Chemical Company, and aramid (Kevlar) available from E. I.du Pont de Nemours and Company, Inc. may be used in conjunction withthis invention to manufacture prepregs.

The prepregs can comprise about 20 to about 50 weight percent,preferably about 25 to about 40 weight percent, of the thermosettableresin compositions of this invention, and about 50 to about 80 weightpercent, preferably about 60 to about 75 weight percent, of continuousfibers such as mentioned above, of which high strength thermally stablefibers such as carbon, boron or glass are preferred. Such fibers arecoated with the thermosettable resin compositions of this invention as ahot melt or solution using processing conditions known in the art.

Composites comprising a multiplicity of continuous fibers can then beprepared from the prepregs by any method known in the art. For example,such composites can be prepared by stacking layer upon layer of thefiber prepregs, where applicable, in the same or opposite direction toprovide a mat or dispersion where applicable, of desired thickness andwhich are cured in stages as generally described herein. Curing isgenerally carried out at 180° C. for two hours under vacuum and about 80psi, then at 230° C. for two hours under free standing conditions, thenat 250° C. for five hours under free standing conditions. Of course,other curing schedules may be employed, depending upon the particularfibers employed in prepreg manufacture, and the specific composite enduses contemplated.

Examples of applications for fiber reinforced composites fabricated fromprepregs comprising thermosettable resin compositions of this inventioninclude the manufacture of primary, secondary and empennage structuresfor both commercial and military aircraft. Such composites are alsouseful in other aerospace applications where there are demands for heatresistant products lighter in weight and longer lasting than basicmaterials such as metal, aluminum and titanium. Similarly, suchcomposites may also be employed in the manufacture of products for theautomobile and electronics industry. The wide spectrum of applicationswithin which the invention herein may be useful will be readily apparentto those skilled in the art.

The following examples further illustrate a preferred embodiment of thisinvention. It is to be understood, however, that the invention is not inany way limited thereto.

EXAMPLES XIV-XVII

The following examples illustrate the preparation of thermosettableresin compositions of this invention comprising matrixes of1,3-bis(ortho-propenylphenoxy)propane, and1,3-bis-(isoeugenoxy)-2-hydroxy-propane with Technochemie's Compimide353, a commercially available mixture of amino maleimide, bis-maleimideand chain extended maleimides (reference, Polymer Journal 1983, 15.p.2).

In Example XIV, 66.6 grams (60% weight) of Compimide 353 is melted in aflask equipped with a mechanical stirrer at 80° C. for 20 minutes. Then,11.1 grams (10% weight) of 1,3,-bis(ortho-propenylphenoxy)propane and33.3 grams (30% weight) 1,3-bis-(isoeugenoxy)-2-hydroxy propane is addedto the melt, and the resulting mixture stirred for an additional 20minutes of 80° C. The contents of the flask is poured into a pan,degassed under vacuum of 80° C. for 10 minutes, then poured into a moldfor curing. The resin at this stage is tacky and flows well. Resincuring is accomplished according to the following schedule: 3 hours at130° C., 2 hours at 150° C. and 5 hours at 250° C. A plaque consistingof the cured resin matrix is formed then cut into test specimens.

Examples XV-XVII are repeats of Example XV, except that the weightpercent addition of components is altered according to the followingtable, in addition to stabilizers phenothiazine and hydroquinone beingadded to Examples XVI and XVII in the indicated amounts.

Prior to curing according to the schedule set forth in Example XV above,the resin compositions of Examples XVI-XVII are tacky and flow well.

                  TABLE I                                                         ______________________________________                                                Grams (weight %)                                                              XIV    XV        XVI       XVII                                       ______________________________________                                        Compimide 353                                                                           66.6 (60)                                                                              59.1 (57) 61 (61) 61 (61)                                  1,3-bis(ortho-                                                                          11.1 (10)                                                                              9.8 (9.5) 18.3 (18.3)                                                                           18.3 (18.3)                              propenyl-phe-                                                                 noxy)propane                                                                  1,3-bis-(isoeu-                                                                         33.3 (30)                                                                              34.5 (33.4)                                                                             18.3 (18.3)                                                                           18.3 (18.3)                              genox)y-2-hy-                                                                 droxy propane                                                                 phenothiazine                        2 (2)                                    hydroquinone                 2 (2)                                            ______________________________________                                    

EXAMPLES XVIII-XXV

The following examples illustrate the preparation of other preferredpolyfunctional maleimide-based thermosettable resin compositions of thisinvention.

In Example XVIII, a mixture of 53 grams (59 weight %) ofN,N'-4,4'-diphenylmethane-bis-maleimide and 37 grams (41 weight %) ofα,α'-bis(ortho-propenylphenoxy)meta-xylene are melted together at 130°C. for one hour. The homogeneous melt is tacky at temperatures above 30° C. and has good flow properties. The mixture is then cured in a moldaccording to the following schedule: 5 hours at 130° C., 2 hours at 180°C., 2 hours at 230° C. and 5 hours at 250° C.

In Example XIX, a mixture of 12 grams (36 weight %) of Compimide 353, 8grams (24 % weight) N,N'-4,4'-diphenylmethane-bis-maleimide, 13 grams(39 weight %) α,α'-bis-(ortho-propenylphenoxy)meta-xylene and 0.07 gramshydroquinone are melted together and cured according to the schedule setforth in XVIII.

In Example XX, a mixture of 5.3 grams (64 weight %) Compimide 353 and 3grams (36 weight %) α,α'-bis(ortho-propenylphenoxy)meta-xylene aremelted and cured together according to the schedule set forth in XVIII.

Example XXI is prepared from a mixture of 31 grams (37 weight %) ofα,α'-bis(ortho-propenylphenoxy)para-xylene and 51.8 grams (63% weight)Compimide-353 which is melted together at 120° C. for 10 minutes,degassed, then cured in a mold according to the schedule described inXVIII.

In Example XXII, 3.1 grams (35 weight %)α,α'-bis(ortho-propenylphenoxy)para-xylene, 5.2 grams (59% weight)Compimide 353, and 0.50 grams (6% weight) aminopropyl terminateddimethyl diloxane (MW=30,000), a reactive rubber compound, are mixed andcured together according to the schedule set out in XVIII.

In Example XXIII, a mixture of 53 grams (59% weight)N,N'-4,4'-diphenylmethane-bis-maleimide and 37 grams (41%weight)α,α'-bis-(2-propenylphenoxy)-meta-xylene is melted together at130° C. for one hour. The homogeneous melt is tacky above temperaturesof 30° C. and has a good flow property. The mixture is then curedaccording to the schedule described in Example XVIII.

Example XVIV is prepared from a mixture of 12 grams (36% weight)Compimide 353, 8 grams (24% weight)N,N'-4,4'-diphenylmethane-bis-maleimide (commercially available asCiba-Geigy's XV-292A), 13 grams (39% weight)α,α'-bis-(2-propenylphenoxy)-meta-xylene and 1% weight hydroquinone as astabilizer, which are melted together and then cured according to theschedule set out in XVIII.

Example XXV is prepared from a mixture of 5.3 grams (63% weight)Compimide 353, 3 grams (36% weight)α,α'-bis-(2-propenylphenoxy)-meta-xylene and 1% weight hydroquinonewhich are melted together and subsequently cured according to theschedule described in XVIII.

Table 2 below summarizes the preparation of Examples XVIII-XXV asdescribed below.

                                      TABLE 2                                     __________________________________________________________________________                Grams (% weight)                                                              XVIII                                                                             XIX XX  XXI  XXII                                                                              XXIII                                                                             XXIV                                                                              XXV                                  __________________________________________________________________________    Compimide 353   12 (36)                                                                           5.3 (64)                                                                          51.8 (63)                                                                          5.2 (59)                                                                              12 (36)                                                                           5.3 (63)                             N,N'-4,4'-diphenyl-                                                                       53 (59)                                                                            8 (24)          53 (59)                                                                            8 (24)                                  methane-bis-                                                                  maleimide                                                                     α,α'-bis(ortho-propenyl                                                       37 (41)                                                                           13 (39)                                                                             3 (36)                                                  phenoxy)-meta-xylene                                                          α,α'-bis(ortho-propenyl-                                                                   31 (37)                                                                           3.1 (35)                                         phenoxy)-para-xylene                                                          α,α'-bis-2-propenyl- 37 (41)                                                                           13 (39)                                                                             3 (36)                             phenoxy-meta-xylene                                                           hydroquinone                         (1) (1)                                  aminopropyl terminated       0.5 (6)                                          dimethyl siloxane                                                             (MW = 30,000)                                                                 __________________________________________________________________________

I claim:
 1. A thermosettable resin composition comprising(a) at least one polyfunctional maleimide compound selected from the group consisting of (i) bis-maleimide and (ii) polymaleimide, having the respective general formulas: ##STR6## where A is a divalent organic radical of at least two carbon atoms and R₁ -R₁₀ are the same or different hydrogen atoms, halogen atoms, cyano groups, straight-chain or branched, saturated or unsaturated alkyl radicals having from 1 to 6 carbon atoms, phenyl radicals or substituted phenyl radicals having one or more substituents selected from straight-chain or branched, substituted or unsubstituted alkyl radicals, halogen atoms or, cyano groups, and where n is a positive integer; and, (b) at least one ether derivative of alkenylphenol selected from the group consisting of compounds having the general formula: ##STR7## where X is

    --CH═CH--R, or

    --CH.sub.2 --CH═CH--R, and

where Y is ##STR8## and where R is defined as R₁ -R₁₀ in formulas (i) and (ii) above, and where R' is either a divalent organic radical of at least two carbon atoms selected from aliphatic, alicyclic, aromatic or heterocyclic radicals or a divalent organic radical of the general formula: ##STR9## and where R is defined as R₁ -R₁₀ in formulas (i) and (ii) above, and where n is a positive integer; and where the oxygen atom that connects Y and the aromatic ring can also be replaced by a sulfur atom.
 2. A composition according to claim 1 wherein (a) is N,N'-4,4'-diphenylmethane-bis-maleimide.
 3. A composition according to claim 1 wherein (b) is α,α'-bis-(ortho-propenylphenoxy)-para-xylene.
 4. A composition according to claim 1 wherein (b) is α,α'-bis-(2-propenylphenoxy)-meta-xylene.
 5. A composition as claimed in claim 1 wherein the weight percent ratio of polyfunctional maleimide compound to ether derivative of alkenylphenol is from about 0.5: 1 to about 10:1.
 6. The composition as claimed in claim 1 wherein the weight percent ratio of polyfunctional maleimide compound to ether derivative of alkenylphenol is from about 1.3:1 to about 2:1. 